Lattice dynamical study of optical modes in Tl2Mn2O7 and In2Mn2O7 pyrochlores

TL;DR

This study investigates the vibrational optical modes of Tl2Mn2O7 and In2Mn2O7 pyrochlores using Raman, IR, and force field analysis, revealing unique spectral features and force constants influenced by orbital hybridization.

Contribution

It provides a detailed force field analysis and mode assignment for Tl2Mn2O7 and In2Mn2O7 pyrochlores, highlighting spectral differences and hybridization effects.

Findings

Higher Mn-O and A-O force constants in these pyrochlores.

Spectral and force field changes are linked to orbital hybridization.

Frequencies closely match observed IR and Raman spectra.

Abstract

The Raman, IR and force field have been investigated for A2Mn2O7 (A= Tl, In) by means of a short-range force constant model which includes four stretching and four bending force constants. Unusual spectral and force field changes are observed and analyzed. The stretching force constant Mn-O and A-O, are found to be relatively higher than those of other pyrochlore oxides of the A2Mn2O7 family, while the remaining force constant values are significantly smaller, especially for Tl2Mn2O7. This trend may be due to strong hybridization of the Tl (6s) orbital with O (2p) and Mn (3d). The assignment of all the modes has been proposed and potential energy distribution is also reported. The evaluated frequencies are close to the available observed infrared and Raman frequencies, giving further support to the present assignments.